CN113698358A - Method for synthesizing quinazolinone compound under induction of visible light - Google Patents
Method for synthesizing quinazolinone compound under induction of visible light Download PDFInfo
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- -1 quinazolinone compound Chemical class 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000006698 induction Effects 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- PXBFMLJZNCDSMP-UHFFFAOYSA-N ortho-aminobenzoylamine Natural products NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229960000583 acetic acid Drugs 0.000 claims abstract description 18
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical class C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 28
- 238000001228 spectrum Methods 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 238000004809 thin layer chromatography Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- NXSVNPSWARVMAY-UHFFFAOYSA-N 1-benzothiophene-2-carbaldehyde Chemical compound C1=CC=C2SC(C=O)=CC2=C1 NXSVNPSWARVMAY-UHFFFAOYSA-N 0.000 description 1
- CTOUNZIAEBIWAW-UHFFFAOYSA-N 3,4-dihydro-1h-quinazolin-2-one Chemical compound C1=CC=C2NC(=O)NCC2=C1 CTOUNZIAEBIWAW-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KIMWOULVHFLJIU-UHFFFAOYSA-N N-Methylanthranilamide Chemical compound CNC(=O)C1=CC=CC=C1N KIMWOULVHFLJIU-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
- C07D239/88—Oxygen atoms
- C07D239/91—Oxygen atoms with aryl or aralkyl radicals attached in position 2 or 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention provides a method for synthesizing a quinazolinone compound by visible light induction, which takes an anthranilamide compound (I) and an aldehyde compound (II) as raw materials, takes glacial acetic acid as a solvent, and reacts under the irradiation of violet light to obtain the quinazolinone compound (III). The method for synthesizing the quinazolinone compound by visible light induction provided by the invention has the advantages of mild reaction conditions, simple and convenient post-treatment operation, no need of additional additives, high reaction efficiency, wide substrate adaptability, high product purity and environmental friendliness.
Description
Technical Field
The invention belongs to the technical field of synthesis, and particularly relates to a method for synthesizing a quinazolinone compound under the induction of visible light.
Background
Quinazolinone is an important nitrogen-containing heterocyclic compound, the parent nucleus structure of the quinazolinone is widely existed in natural products and artificially synthesized drugs, and the quinazolinone has rich physiological and pharmacological activities, such as anti-tumor, anti-virus, anti-inflammatory, anti-infection, anti-depression and the like, and has important research value in the field of medicine.
Due to their rich pharmacological activity, the synthesis and utilization of quinazolinone compounds have received a great deal of attention from chemists and biologists. The traditional quinazolinone synthesis method mainly adopts metal catalytic heating reaction. These methods often require harsh reaction conditions, and in addition, the addition of strong oxidants (such as potassium persulfate) and metal catalysts (such as palladium acetate, copper oxide) and the like results in the presence of metal residues in the product, requiring cumbersome separation and purification steps. The photochemical reaction developed recently uses light as an energy source, is more green and environment-friendly than the traditional heating reaction, but the photochemical reaction reported at present still needs to add a photocatalyst to achieve the ideal reaction effect, and the defect that an additive cannot be used is avoided.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel method for synthesizing quinazolinone compound under the induction of visible light, aiming at the defects in the prior art, and the high-efficiency reaction can be realized without adding a photocatalyst.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for synthesizing a quinazolinone compound by visible light induction comprises the following steps: the method comprises the following steps of taking an anthranilamide compound (I) and an aldehyde compound (II) as raw materials, taking glacial acetic acid as a solvent, and reacting under ultraviolet irradiation to obtain a quinazolinone compound (III), wherein the reaction formula is as follows:
wherein: r1Is H or methyl; r2Is substituted phenyl or substituted heterocycle;
the substituted phenyl is a para-substituted benzene ring, and the substituent is selected from hydroxyl, methyl, cyano and chlorine;
the substituted heterocycle is selected from 3-pyridyl, 4-pyridyl, benzo-2-thienyl.
As a preferable aspect of the present invention, the violet light source is selected from an LED (light emitting diode) or CFL (compact fluorescent lamp) light source.
According to the scheme, the power of the purple light is 5-20W, and the wavelength of the purple light is 390-400 nm.
According to the scheme, the molar ratio of the anthranilamide compound (I) to the aldehyde compound (II) is 1: 1-5, preferably 1: 1.1.
according to the scheme, the concentration of the anthranilamide compound (I) in the obtained solution after the anthranilamide compound (I) is dissolved in the solvent is 0.1-3 mol/L, and preferably 0.1 mol/L.
According to the scheme, the reaction temperature is 20-200 ℃, and preferably 20-30 ℃; the reaction time is 12-24 hours, preferably 16 hours.
According to the scheme, the method for synthesizing the quinazolinone compound by visible light induction comprises the following specific steps: adding anthranilamide compounds (I) and aldehyde compounds (II) into glacial acetic acid, reacting under ultraviolet irradiation, monitoring by TLC to obtain a reaction solution, adding distilled water (to facilitate product precipitation), stirring, filtering, washing the obtained solid with water, and vacuum drying to obtain quinazolinone compounds (III).
The basic reaction principle of the invention is as follows: in the reaction system, acetic acid is used as a solvent and also used as a catalyst, an anthranilamide compound and aldehyde are firstly dehydrated and condensed under the catalysis of the acetic acid to form a dihydroquinazolinone intermediate, the intermediate absorbs purple light in the reaction system taking the acetic acid as the solvent to serve as an energy source, and oxygen in the air serves as an oxidant to be dehydrogenated to form a quinazolinone target product.
Has the advantages that: compared with the prior art, the method for synthesizing the quinazolinone compound by visible light induction has the advantages of mild reaction conditions (the reaction can be carried out at room temperature), simple and convenient post-treatment operation, no need of additional additives, high reaction efficiency (the yield reaches 75-93%), wide substrate adaptability, high product purity and environmental protection.
Drawings
FIG. 1 is a hydrogen spectrum of the product obtained in example 1;
FIG. 2 is a carbon spectrum of the product obtained in example 1;
FIG. 3 is a hydrogen spectrum of the product obtained in example 2;
FIG. 4 is a carbon spectrum of the product obtained in example 2;
FIG. 5 is a hydrogen spectrum of the product obtained in example 3;
FIG. 6 is a carbon spectrum of the product obtained in example 3;
FIG. 7 is a hydrogen spectrum of the product obtained in example 4;
FIG. 8 is a carbon spectrum of the product obtained in example 4;
FIG. 9 is a hydrogen spectrum of the product obtained in example 5;
FIG. 10 is a carbon spectrum of the product obtained in example 5;
FIG. 11 is a hydrogen spectrum of the product obtained in example 6;
FIG. 12 is a carbon spectrum of the product obtained in example 6;
FIG. 13 is a hydrogen spectrum of the product obtained in example 7;
FIG. 14 is a carbon spectrum of the product obtained in example 7;
FIG. 15 is a hydrogen spectrum of the product obtained in example 8;
FIG. 16 is a carbon spectrum of the product obtained in example 8.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further illustrated in detail by the following examples.
Example 1
A method for synthesizing the following quinazolinone compound under the induction of visible light comprises the following specific steps:
adding 2-amino-N-methylbenzamide (0.2mmol), p-methylbenzaldehyde (0.22mmol) and glacial acetic acid (2 mL) into a 10mL reaction bottle, uniformly stirring, stirring the obtained reaction solution at room temperature for 16 hours under the irradiation of a 5W violet LED lamp (with the violet wavelength of 390-400 nm), detecting the reaction completion by TLC, adding 10mL of distilled water into the reaction solution, stirring at room temperature for 10 minutes, filtering, washing the obtained solid with water for three times, 3mL each time, and then drying in vacuum at 40 ℃ for 6 hours to obtain a white solid, namely the target product, wherein the yield is 78%.
The hydrogen spectrogram and the carbon spectrogram of the obtained product are respectively shown in fig. 1 and fig. 2, nuclear magnetism shows that no impurities exist, the purity can be determined to be more than 95%, and the structural characterization data is as follows: 1H NMR (500MHz, Chloroform-d) δ 8.32 (d, J ═ 7.4Hz,1H),7.74(dd, J ═ 1.7,5.9Hz,2H), 7.51-7.44 (m,3H),7.32(d, J ═ 7.8Hz,2H),3.50(s,3H),2.43(s,3H).13C NMR(126MHz,Chloroform-d) δ162.7,156.2,147.2,140.2,134.1,132.4,129.4,127.9,127.3,126.8,126.5,120.3,34.2, 21.3.)
Example 2
A method for synthesizing the following quinazolinone compound under the induction of visible light comprises the following specific steps:
adding 2-aminobenzamide (0.2mmol), p-tolualdehyde (0.22mmol) and 2mL of glacial acetic acid into a 10mL reaction bottle, uniformly stirring, stirring the obtained reaction solution at room temperature for 16 hours under the irradiation of a 5W purple light LED lamp, adding 10mL of distilled water into the reaction solution after the reaction is completely detected by TLC (thin layer chromatography), stirring at room temperature for 10 minutes, filtering, washing the obtained solid with water for three times, 3mL each time, and then drying in vacuum at 40 ℃ for 6 hours to obtain a white solid, namely the target product, wherein the yield is 78%.
The hydrogen spectrogram and the carbon spectrogram of the obtained product are respectively shown in fig. 3 and fig. 4, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO-d6)δ12.47(s,1H),8.15(d,J＝7.9Hz,1H), 8.10(d,J＝8.3Hz,2H),7.83(t,J＝6.9Hz,1H),7.73(d,J＝8.0Hz,1H),7.51 (t,J＝7.4Hz,1H),7.35(d,J＝8.0Hz,2H),2.39(s,3H).13C NMR(126MHz, DMSO-d6)δ162.7,152.7,149.3,141.9,135.0,130.4,129.6,128.1,127.9,126.8,126.3, 121.4,21.5.
comparative example 1
The solvent glacial acetic acid from example 2 was replaced by an equal volume of other solvents for comparison, the solvents used and the reaction yields are shown in table 1 below.
TABLE 1
As can be seen from table 1, the use of glacial acetic acid as a solvent can greatly improve the reaction efficiency.
Example 3
A method for synthesizing the following quinazolinone compound under the induction of visible light comprises the following specific steps:
adding 2-aminobenzamide (0.2mmol), p-hydroxybenzaldehyde (0.22mmol) and 2mL of glacial acetic acid into a 10mL reaction bottle, uniformly stirring, stirring the obtained reaction solution at room temperature for 16 hours under the irradiation of a 5W purple light LED lamp, adding 10mL of distilled water into the reaction solution after the TLC detection reaction is completed, stirring at room temperature for 10 minutes, filtering, washing the obtained solid with water for three times, 3mL each time, and then drying in vacuum at 40 ℃ for 6 hours to obtain a white solid, namely the target product, wherein the yield is 85%.
The hydrogen spectrogram and the carbon spectrogram of the obtained product are respectively shown in fig. 5 and 6, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO-d6)δ12.29(s,1H),10.14(s,1H),8.15-8.06 (m,3H),7.83-7.76(m,1H),7.68(d,J＝8.0Hz,1H),7.46(t,J＝7.4Hz,1H), 6.89(d,J＝8.6Hz,2H).13C NMR(126MHz,DMSO-d6)δ162.3,160.5,152.1, 149.0,134.5,129.6,127.2,125.9,125.8,123.2,120.6,115.3.
example 4
A method for synthesizing the following quinazolinone compound under the induction of visible light comprises the following specific steps:
adding 2-aminobenzamide (0.2mmol), p-cyanobenzaldehyde (0.22mmol) and 2mL of glacial acetic acid into a 10mL reaction bottle, uniformly stirring, stirring the obtained reaction solution at room temperature for 16 hours under the irradiation of a 5W purple light LED lamp, adding 10mL of distilled water into the reaction solution after the reaction is completely detected by TLC (thin layer chromatography), stirring at room temperature for 10 minutes, filtering, washing the obtained solid with water for three times, 3mL each time, and then drying in vacuum at 40 ℃ for 6 hours to obtain a white solid, namely the target product, wherein the yield is 87%.
The hydrogen spectrogram and the carbon spectrogram of the obtained product are respectively shown in fig. 7 and fig. 8, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO-d6)δ12.70(s,1H),8.35(d,J＝8.5Hz,2H), 8.19(d,J＝7.6Hz,1H),8.04(d,J＝8.5Hz,2H),7.91-7.84(m,1H),7.79(d, J＝8.1Hz,1H),7.58(t,J＝7.4Hz,1H).13C NMR(126MHz,DMSO-d6)δ162.1, 151.0,148.3,136.9,134.7,132.5,128.6,127.7,127.2,125.9,121.2,118.3,113.6.
example 5
A method for synthesizing the following quinazolinone compound under the induction of visible light comprises the following specific steps:
adding 2-aminobenzamide (0.2mmol), p-chlorobenzaldehyde (0.22mmol) and 2mL of glacial acetic acid into a 10mL reaction bottle, uniformly stirring, stirring the obtained reaction solution at room temperature for 16 hours under the irradiation of a 5W purple light LED lamp, adding 10mL of distilled water into the reaction solution after the TLC detection reaction is completed, stirring at room temperature for 10 minutes, filtering, washing the obtained solid with water for three times, 3mL each time, and then drying in vacuum at 40 ℃ for 6 hours to obtain a white solid, namely the target product, wherein the yield is 81%.
The hydrogen spectrum and the carbon spectrum of the obtained product are respectively shown in fig. 9 and fig. 10, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO-d6)δ12.61(s,1H),8.20(d,J＝8.3Hz,2H), 8.17(d,J＝7.0Hz,1H),7.88-7.81(m,1H),7.76(d,J＝8.0Hz,1H),7.63(d, J＝8.6Hz,2H),7.54(t,J＝7.4Hz,1H).13C NMR(126MHz,DMSO-d6)δ162.2, 151.4,148.6,136.3,134.7,131.6,129.6,128.7,127.6,126.8,125.9,121.0.
example 6
A method for synthesizing the following quinazolinone compound under the induction of visible light comprises the following specific steps:
adding 2-aminobenzamide (0.2mmol), 3-pyridine formaldehyde (0.22mmol) and 2mL glacial acetic acid into a 10mL reaction bottle, uniformly stirring, stirring the obtained reaction solution at room temperature for 16 hours under the irradiation of a 5W purple light LED lamp, adding 10mL distilled water into the reaction solution after the TLC detection reaction is completed, stirring at room temperature for 10 minutes, filtering, washing the obtained solid with water for three times, 3mL each time, and then drying in vacuum at 40 ℃ for 6 hours to obtain a white solid, namely the target product, wherein the yield is 93%.
The hydrogen spectrum and the carbon spectrum of the obtained product are respectively shown in fig. 11 and fig. 12, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO-d6)δ12.72(s,1H),9.29(d,J＝2.4Hz,1H), 8.75(dd,J＝1.6,4.8Hz,1H),8.49(dt,J＝2.0,8.0Hz,1H),8.17(dd,J＝1.5,7.9 Hz,1H),7.89–7.82(m,1H),7.77(d,J＝8.0Hz,1H),7.61-7.52(m,2H).13C NMR(126MHz,DMSO-d6)δ162.2,151.8,150.9,148.8,148.5,135.4,134.7,128.8, 127.5,127.0,125.9,123.6,121.1.
example 7
A method for synthesizing the following quinazolinone compound under the induction of visible light comprises the following specific steps:
adding 2-aminobenzamide (0.2mmol), 4-pyridinecarboxaldehyde (0.22mmol) and 2mL glacial acetic acid into a 10mL reaction bottle, uniformly stirring, stirring the obtained reaction solution at room temperature for 16 hours under the irradiation of a 5W purple light LED lamp, adding 10mL distilled water into the reaction solution after the TLC detection reaction is completed, stirring at room temperature for 10 minutes, filtering, washing the obtained solid with water for three times, 3mL each time, and then drying in vacuum at 40 ℃ for 6 hours to obtain a white solid, namely the target product, wherein the yield is 76%.
The hydrogen spectrum and the carbon spectrum of the obtained product are respectively shown in fig. 13 and fig. 14, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO-d6)δ12.77(s,1H),8.81-8.76(m,2H),8.18 (dd,J＝1.5,7.9Hz,1H),8.14-8.07(m,2H),7.91-7.84(m,1H),7.79(d,J＝ 8.0Hz,1H),7.62–7.55(m,1H).13C NMR(126MHz,DMSO-d6)δ162.1,150.5, 150.3,148.2,139.9,134.8,127.7,127.4,125.9,121.6,121.5.
example 8
A method for synthesizing the following quinazolinone compound under the induction of visible light comprises the following specific steps:
adding 2-aminobenzamide (0.2mmol), benzothiophene-2-formaldehyde (0.22mmol) and glacial acetic acid (2 mL) into a 10mL reaction bottle, uniformly stirring, stirring the obtained reaction solution at room temperature for 16 hours under the irradiation of a 5W purple light LED lamp, detecting the reaction completion by TLC, adding 10mL distilled water into the reaction solution, stirring at room temperature for 10 minutes, filtering, washing the obtained solid with water for three times (3 mL each time), and then drying in vacuum at 40 ℃ for 6 hours to obtain a white solid, namely the target product, wherein the yield is 76%.
The hydrogen spectrum and the carbon spectrum of the obtained product are respectively shown in fig. 15 and fig. 16, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO-d6)δ12.87(s,1H),8.58(s,1H),8.16(d, J＝7.8Hz,1H),8.05(d,J＝7.8Hz,1H),7.94(d,J＝7.7Hz,1H),7.88-7.81(m, 1H),7.71(d,J＝8.1Hz,1H),7.57-7.42(m,2H).13C NMR(126MHz,DMSO-d6) δ161.6,148.3,147.9,140.7,139.4,137.5,134.8,127.2,126.9,126.7,126.3,126.0, 125.2,125.1,122.6,121.2。
Claims (6)
1. a method for synthesizing a quinazolinone compound under the induction of visible light is characterized by comprising the following steps: the method comprises the following steps of taking an anthranilamide compound (I) and an aldehyde compound (II) as raw materials, taking glacial acetic acid as a solvent, and reacting under ultraviolet irradiation to obtain a quinazolinone compound (III), wherein the reaction formula is as follows:
wherein: r1Is H or methyl; r2Is substituted phenyl or substituted heterocycle;
the substituted phenyl is a para-substituted benzene ring, and the substituent is selected from hydroxyl, methyl, cyano and chlorine;
the substituted heterocycle is selected from 3-pyridyl, 4-pyridyl, benzo-2-thienyl.
2. The method for the visible light-induced synthesis of quinazolinone compounds according to claim 1, characterized in that the violet light source is selected from LED or CFL light source, the violet light power is 5-20W, and the violet light wavelength is 390-400 nm.
3. The visible light-induced synthesis method of quinazolinone compound according to claim 1, wherein the molar ratio of anthranilamide compound (I) to aldehyde compound (II) is 1: 1 to 5.
4. The method for visible light-induced synthesis of quinazolinone compounds according to claim 1, wherein the concentration of anthranilamide compound (I) in the solution obtained after dissolving in solvent is 0.1-3 mol/L.
5. The method for visible light-induced synthesis of quinazolinone compounds according to claim 1, characterized in that the reaction temperature is 20-200 ℃ and the reaction time is 12-24 hours.
6. The method for the visible light-induced synthesis of quinazolinone compounds according to claim 1, characterized by comprising the following steps: adding anthranilamide compound (I) and aldehyde compound (II) into glacial acetic acid, reacting under ultraviolet irradiation, monitoring by TLC to obtain a reaction solution, adding distilled water into the reaction solution, stirring thoroughly, filtering, washing the obtained solid with water, and vacuum drying to obtain quinazolinone compound (III).
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